Silicon in nature

A77. M. G. Voronkov, G. I. Zelchan, and E. Ya. Lukevits, " Kremnii i Zhizn . Zinatne, Riga, 1971. 327 pp. This is a comprehensive book on Silicon and Life. Part 1 (2571) covers silicon in nature and Part 2 (2564) the biological action of silicon compounds. Most of the references are to the biochemical and medical literature. 

It follows that the oxides, nitrides, borides, carbides, and silicides (not to be confused with silicates) of all metals and NMESs are ceramics which, needless to say, leads to a vast number of compounds. This number becomes even more daunting when it is appreciated that the silicates are also, by definition, ceramics. Because of the abundance of oxygen and silicon in nature, silicates are ubiquitous rocks, dust, clay, mud, mountains, sand — in short, the vast majority of the earth s crust — are composed of silicate-based minerals. When it is also appreciated that even cement, bricks, and concrete are essentially silicates, the case could be made that we live in a ceramic world. 

Silicon has a luster but does not exhibit metallic properties. Most silicon in nature is a silicon oxide, which occurs in sand and quartz, which is shown here. 

The +4 oxidation state (z = 4) is the only important one in the chemistry of silicon in naturally occurring systems [10], and the coordination number of silicon, N, is most often four. Compared to transition metals discussed in the previous chapter, silicon is generally less electropositive, e.g., the partial positive charge on silicon nucleophilic attack, and since N = z, coordination expansion does not spontaneously occur with nucleophilic reagents. These factors make the kinetics of hydrolysis and condensation considerably slower than observed in transition metal systems or in Group III systems. 

Silicon makes up 25.7% of the earth s crust, by weight, and is the second most abundant element, being exceeded only by oxygen. Silicon is not found free in nature, but occurs chiefly as the oxide and as silicates. Sand, quartz, rock crystal, amethyst, agate, flint, jasper, and opal are some of the forms in which the oxide appears. Granite, hornblende, asbestos, feldspar, clay, mica, etc. are but a few of the numerous silicate minerals. 

In the geochemistry of fluorine, the close match in the ionic radii of fluoride (0.136 nm), hydroxide (0.140 nm), and oxide ion (0.140 nm) allows a sequential replacement of oxygen by fluorine in a wide variety of minerals. This accounts for the wide dissemination of the element in nature. The ready formation of volatile silicon tetrafluoride, the pyrohydrolysis of fluorides to hydrogen fluoride, and the low solubility of calcium fluoride and of calcium fluorophosphates, have provided a geochemical cycle in which fluorine may be stripped from solution by limestone and by apatite to form the deposits of fluorspar and of phosphate rock (fluoroapatite [1306-01 -0]) approximately CaF2 3Ca2(P0 2 which ate the world s main resources of fluorine (1). 

Silicon [7440-21-3] Si, from the Latin silex, silicis for flint, is the fourteenth element of the Periodic Table, has atomic wt 28.083, and a room temperature density of 2.3 gm /cm. SiUcon is britde, has a gray, metallic luster, and melts at 1412°C. In 1787 Lavoisier suggested that siUca (qv), of which flint is one form, was the oxide of an unknown element. Gay-Lussac and Thenard apparently produced elemental siUcon in 1811 by reducing siUcon tetrafluoride with potassium but did not recognize it as an element. In 1817 BerzeHus reported evidence of siUcon occurring as a precipitate in cast iron. Elemental siUcon does not occur in nature. As a constituent of various minerals, eg, siUca and siUcates such as the feldspars and kaolins, however, siUcon comprises about 28% of the earth s cmst. There are three stable isotopes that occur naturally and several that can be prepared artificially and are radioactive (Table 1) (1). 

Silicon, a low density chemical element having nonmetallic chaiacteristics, is the second, after oxygen (50.5%), most abundant element in the lithosphere. Silicon occurs naturally in the form of oxides and silicates and constitutes over 25% of the earth s cmst (see Silica). 

Other limitations on phytoplankton growth are chemical in nature. Nitrogen, in the form of nitrate, nitrite and ammonium ions, forms a basic building material of a plankton s cells. In some species silicon, as silicate, takes on this role. Phosphorus, in the form of phosphate, is in both cell walls and DNA. Iron, in the form of Fe(III) hydroxyl species, is an important trace element. Extensive areas of the mixed layer of the upper ocean have low nitrate and phosphate levels during... 

Boron (like silicon) invariably occurs in nature as 0X0 compounds and is never found as the element or even directly bonded to any other element than oxygen. The structural chemistry of B-O compounds is characterized by an extraordinary complexity and diversity which rivals those of the borides (p. 145) and boranes (p. 151). In addition, vast numbers of predominantly organic compounds containing B-O are known. 

Silicon never occurs free it invariably occurs combined with oxygen and, with trivial exceptions, is always 4-coordinate in nature. The Si04 unit may occur as an individual group or be linked into chains, ribbons, rings, sheets or three-dimensional frameworks (pp. 347-59). 

Gmelin Handbook of Inorganic Chemistry, 8th edn., Springer-Verlag, Berlin, Silicon Suppl. B2, 1984, 312 pp. See also Suppl. Bl, 1986, 545 pp. for further information on occurrence of SiC in nature, its manufacture, chemical reactions, applications, etc. 

Silicon is the second most abundant element in the earth s crust. It occurs in sand as the dioxide Si02 and as complex silicate derivatives arising from combinations of the acidic oxide Si02 with various basic oxides such as CaO, MgO, and K20. The clays, micas, and granite, which make up most soils and rocks, are silicates. All have low solubility in water and they are difficult to dissolve, even in strong acids. Silicon is not found in the elemental state in nature. 

Murnane, R. J. and Stallard, R. F. (1990). Germanium and silicon in rivers of the Orinoco drainage basin, Venezuela and Colombia. Nature 344, 749-752. 

In this chapter we describe the basic principles involved in the controlled production and modification of two-dimensional protein crystals. These are synthesized in nature as the outermost cell surface layer (S-layer) of prokaryotic organisms and have been successfully applied as basic building blocks in a biomolecular construction kit. Most importantly, the constituent subunits of the S-layer lattices have the capability to recrystallize into iso-porous closed monolayers in suspension, at liquid-surface interfaces, on lipid films, on liposomes, and on solid supports (e.g., silicon wafers, metals, and polymers). The self-assembled monomolecular lattices have been utilized for the immobilization of functional biomolecules in an ordered fashion and for their controlled confinement in defined areas of nanometer dimension. Thus, S-layers fulfill key requirements for the development of new supramolecular materials and enable the design of a broad spectrum of nanoscale devices, as required in molecular nanotechnology, nanobiotechnology, and biomimetics [1-3]. 

Silicon w is first isolated and described as an element in 1824 by Jdns Jacob Berzelius, a Swedish chemist. Silicon does not occur uncombined in nature, i.e.- as an element. It is found in practically aU rocks as well as in sand, clays, and soils, combined either with oxygen as silica (Si02= silicon dioxide) or with oxygen plus other elements (e.g., aliuninum, mcignesium, calcium, sodium, potassium, or iron) as silicates. Its compounds also occur in all natural waters, in the atmosphere (as siliceous dust), in many plants, and in the skeletons, tissues, and body fluids of some animals. 

The insertion of the oxygen atoms widens the silicon lattice considerably. A relatively large void remains in each of the four vacant octants of the unit cell. In natural cristobalite they usually contain foreign ions (mainly alkali and alkaline earth metal ions) that probably stabilize the structure and allow the crystallization of this modification at temperatures far below the stability range of pure cristobalite. To conserve electrical neutrality, probably one Si atom per alkali metal ion is substituted by an A1 atom. The substitution of Si... 

Tetravalent silicon is the only structural feature in all silicon sources in nature, e.g. the silicates and silica even elemental silicon exhibits tetravalency. Tetravalent silicon is considered to be an ana-logon to its group 14 homologue carbon and in fact there are a lot of similarities in the chemistry of both elements. Furthermore, silicon is tetravalent in all industrially used compounds, e.g. silanes, polymers, ceramics, and fumed silica. Also the reactions of subvalent and / or low coordinated silicon compounds normally lead back to tetravalent silicon species. It is therefore not surprising that more than 90% of the relevant literature deals with tetravalent silicon. The following examples illustrate why "ordinary" tetravalent silicon is still an attractive field for research activities Simple and small tetravalent silicon compounds - sometimes very difficult to synthesize - are used by theoreticians and preparative chemists as model compounds for a deeper insight into structural features and the study of the reactivity influenced by different substituents on the silicon center. As an example for industrial applications, the chemical vapor decomposition (CVD) of appropriate silicon precursors to produce thin ceramic coatings on various substrates may be mentioned. 

Silicon exists in nature only in the most thermodynamically stable form in a oxygen-containing atmosphere. Each silicon atom is surrounded by four oxygen atoms in tetrahedral symmetry. Mankind has used the special stability of such compounds to prepare glass, chinaware, ceramics, and building materials like concrete, etc. Silicates today are still one of the most important materials. 

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